CN102692667A - Polarizing membrane and polarizing film - Google Patents
Polarizing membrane and polarizing film Download PDFInfo
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- CN102692667A CN102692667A CN2012100806076A CN201210080607A CN102692667A CN 102692667 A CN102692667 A CN 102692667A CN 2012100806076 A CN2012100806076 A CN 2012100806076A CN 201210080607 A CN201210080607 A CN 201210080607A CN 102692667 A CN102692667 A CN 102692667A
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- light polarizing
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
- G02B5/3025—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state
- G02B5/3033—Polarisers, i.e. arrangements capable of producing a definite output polarisation state from an unpolarised input state in the form of a thin sheet or foil, e.g. Polaroid
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/14—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length
- B29C39/18—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor for making articles of indefinite length incorporating preformed parts or layers, e.g. casting around inserts or for coating articles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/24—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length
- B29C41/28—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of indefinite length by depositing flowable material on an endless belt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
- B29C55/08—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique transverse to the direction of feed
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2029/00—Use of polyvinylalcohols, polyvinylethers, polyvinylaldehydes, polyvinylketones or polyvinylketals or derivatives thereof as moulding material
- B29K2029/04—PVOH, i.e. polyvinyl alcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0018—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular optical properties, e.g. fluorescent or phosphorescent
- B29K2995/0034—Polarising
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- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Polarising Elements (AREA)
- Liquid Crystal (AREA)
Abstract
The invention relates to a polarizing membrane and a polarizing film. The polarizing membrane according to an embodiment of the present invention includes a polyvinyl alcohol-based resin membrane containing a dichromatic substance. The polyvinyl alcohol-based resin membrane has an Nz coefficient of 1.10 or more and 1.50 or less.
Description
The right of priority that the Japanese patent application that requires to submit on March 23rd, 2011 according to the 119th the application of united states patent law is 2011-063850 number is incorporated herein with for referencial use.
Technical field
The present invention relates to light polarizing film (polarizing membrane) and polarisation diaphragm (polarizing film).
Background technology
In the liquid crystal indicator as typical image display device, because its image forms pattern, absolute demand is arranged on the liquid crystal cell both sides with the polarisation diaphragm.The polarisation diaphragm is separately typically through forming at two surperficial laminated protectiveness films of light polarizing film.Light polarizing film typically through uniaxial tension polyvinyl alcohol resin film and this oriented film that dyes produce (referring to, for example, japanese patent application laid is opened Hei10-288709 number and is opened Hei 11-49878 number with japanese patent application laid).Yet each polarisation diaphragm relates to the endurance issues that is described below.The polarisation diaphragm is responsive to the variation of temperature and humidity.Especially, crack owing to temperature variation sharp.
Summary of the invention
Carried out the present invention for solving general issues, fundamental purpose of the present invention is to provide to have gathered the polarisation diaphragm of excellent optical with the permanance of excellence.
According to an aspect of the present invention, a kind of light polarizing film is provided.Said light polarizing film comprises the polyvinyl alcohol resin film that comprises dichroic substance.Said polyvinyl alcohol resin film has more than 1.10 to the Nz coefficient below 1.50.
In one embodiment of the invention, the degree of polarization of said light polarizing film under 40% monolithic transmissivity is more than 99.9%.
In another embodiment of the present invention, said light polarizing film has the thickness less than 10 μ m.
In another embodiment of the present invention, said light polarizing film has the above thickness of 1 μ m.
In another embodiment of the present invention; Said light polarizing film is shunk along first direction through one of polyvinyl alcohol resin layer of making the polyvinyl alcohol resin film and on the thermoplastic resin base material, forming, and makes one of said film and said layer stretch and obtain along second direction.
In another embodiment of the present invention, the shrinkage factor of the said first direction in edge is to below 40% more than 5%.
In another embodiment of the present invention, the draw ratio of the said second direction in edge is more than 4.0 times.
According to a further aspect in the invention, a kind of polarisation diaphragm is provided.Said polarisation diaphragm comprises said light polarizing film and at the protectiveness film of at least one side laminated of said light polarizing film.
Light polarizing film of the present invention is made up of the polyvinyl alcohol resin film that the Nz coefficient falls in the particular range, and its orientation character (state of orientation of polyvinyl alcohol resin molecule) is controlled.Therefore, the polarisation diaphragm of the permanance of having gathered excellent optical and excellence can be provided.Particularly, the use of light polarizing film of the present invention can provide this type of polarisation diaphragm, and it suppresses because the generation of the crackle that temperature variation caused sharp when keeping excellent optical.
Description of drawings
In the accompanying drawings:
Fig. 1 is the figure of the method for the Nz coefficient of explanation calculating PVA resin film;
Fig. 2 is the synoptic diagram of the instantiation of the method for explanation production light polarizing film; With
Fig. 3 is the synoptic diagram of the instantiation of the method for the said production light polarizing film of explanation.
Embodiment
Hereinafter, the preferred embodiments of the invention are described.Yet the present invention is not subject to these embodiments.
(definition of term and symbol)
The definition of term as used herein and symbol is following.
(1) refractive index (nx, ny and nz)
Symbol nx representes the refractive index of the direction (that is, slow-axis direction) that refractive index in the face wherein is maximum, and perpendicular to the refractive index of the direction of slow axis, nz representes the refractive index of thickness direction in the ny presentation surface.
(2) phase differential (Re) in the face
Through phase differential (Re): Re=(nx-ny) * d in the following expression formula acquisition face, wherein d (nm) representes the thickness of film (layer).
(3) thickness direction phase differential (Rth)
Obtain thickness direction phase differential (Rth): Rth={ (nx+ny)/2-nz} * d through following expression formula, wherein the thickness of d (nm) expression film (layer).
(4) Nz coefficient
Obtain Nz coefficient: Nz=(nx-nz)/(nx-ny) through following expression formula.
A. light polarizing film
Light polarizing film of the present invention is made up of the polyvinyl alcohol resin that comprises dichroic substance (hereinafter being called " PVA resinoid ") film.
The instance of dichroic substance comprises iodine and organic dyestuff.Those materials can be used alone or in combination.In those, preferably use iodine.
Any suitable resin can be used as the PVA resinoid that is used to form the PVA resin film.The example comprises polyvinyl alcohol (PVA) and ethylene-vinyl alcohol copolymer.Obtain polyvinyl alcohol (PVA) through the saponification polyvinyl acetate.Obtain ethylene-vinyl alcohol copolymer through the saponification vinyl-vinyl acetate copolymer.The resinoid saponification degree of PVA typically is 85mol% to 100mol%, preferred 95.0mol% to 99.95mol%, more preferably 99.0mol% to 99.93mol%.Saponification degree can be measured according to JIS K 6726-1994.The resinoid use of PVA with this saponification degree can provide the light polarizing film of excellent in te pins of durability.When saponification degree is high, but the resin gelation.
The resinoid average degree of polymerization of PVA can be depending on purpose and suitably selects.Average degree of polymerization typically is 1,000 to 10,000, and is preferred 1,200 to 4,500, and more preferably 1,500 to 4,300.It should be noted that average degree of polymerization can measure according to JIS K 6726-1994.
The Nz coefficient of PVA resin film is preferred more than 1.10.Simultaneously, the Nz coefficient of PVA resin film is preferred below 1.50, more preferably below 1.40.The Nz coefficient is arranged in this scope can provide the polarisation diaphragm with excellent durability when keeping the optical characteristics of light polarizing film.When the Nz coefficient less than 1.10 the time, it is so high that the orientation character (uniaxiality) of PVA resin film becomes, to such an extent as to maybe not can obtain sufficient permanance.When the Nz coefficient surpasses 1.50, maybe not can obtain the for example required display quality of LCD TV.
The Nz coefficient of PVA resin film is the index of orientation character of the strand of PVA resin film, and by the phase difference calculating of PVA resin film.The phase differential of PVA resin film (a value) is through with the mensuration of getting off: changing the phase differential of measuring light polarizing film when measuring wavelength (λ); Drafting as shown in Figure 1 is directed against the phase differential by the light polarizing film of the represented measurement wavelength of abscissa axis; Create curve of approximation based on following equality; And by curve of approximation calculating asymptotic line (a value).Measure the phase differential of light polarizing film here, by its place ahead and vergence direction.
R＝a+b/(λ
2-600
2)
In equality, R representes the phase differential of light polarizing film, and a representes the phase differential of PVA resin film, and b representes constant.
Light polarizing film preferably shows the absorption dichromatism under any wavelength in the wavelength coverage of 380nm to 780nm.The degree of polarization that light polarizing film has under 40% monolithic transmissivity is preferred more than 99.9%, more preferably more than 99.93%, still more preferably more than 99.95%.
The thickness of light polarizing film can be set at any suitable value.Below the preferred 30 μ m of thickness, more preferably below the 25 μ m, still more preferably below the 20 μ m, especially preferably less than 10 μ m.Light polarizing film typically has the convergent force bigger than protectiveness film, and the stress of generation at the interface between light polarizing film and protectiveness film.Therefore, can crack.The convergent force of light polarizing film depends on its thickness, and convergent force reduces and reduces with thickness.Be purchased the light polarizing film that can get and typically have big relatively thickness, about 20 μ m to 25 μ m, so its endurance is insufficient.Yet,, can obtain the light polarizing film of excellent in te pins of durability according to the present invention.In addition, thickness is made as less than 10 μ m can significantly improves permanance.Simultaneously, more than the preferred 1 μ m of thickness.When thickness during, maybe not can obtain sufficient optical characteristics less than 1 μ m.
Light polarizing film of the present invention can be suitable arbitrarily form use.Through at least one side lamination protectiveness film of light polarizing film and typically use light polarizing film (as the polarisation diaphragm).The formation material that is used for the protectiveness film does; For example, (methyl) acrylic resin, cellulosic resin such as diacetyl cellulose or triacetyl cellulose, cycloolefin resinoid, olefine kind resin such as polypropylene, esters resin such as polyethylene terephthalate resinoid, polyamide-based resin, polycarbonate resin or its copolymer resin.It should be noted that following thermoplastic resin base material with description can be used as the protectiveness film and need not processing.
The protectiveness film preferably has the thickness of 20 μ m to 100 μ m.The protectiveness film can pass through bonding coat (particularly, adhesive phase or pressure sensitive adhesive layer) and be laminated on the light polarizing film, but or lamination so that closely contact (through any bonding coat) with light polarizing film.Adhesive phase is formed by any suitable adhesive.Bonding agent does, for example the vinyl alcohol bonding agent.
B. the method for production light polarizing film
Produce light polarizing film of the present invention through any appropriate method, as long as can satisfy the Nz coefficient.Typically, light polarizing film stands to produce like the processing that stretches or dye through suitably making the PVA resin film.
The B-1.PVA resin film
The PVA resin film typically forms with length form (length fashion).The PVA resin film preferably has the thickness less than 100 μ m.For example, the PVA resin film can be the PVA based resin film, or can be the PVA resinoid layer that is formed on the thermoplastic resin base material.During the light polarizing film of the thickness more than production has 10 μ m, preferably use the PVA based resin film.The PVA based resin film preferably has the thickness of 50 μ m to 80 μ m.When production has the light polarizing film less than the thickness of 10 μ m, preferably use the layered product of thermoplastic resin base material and PVA resinoid layer.PVA resinoid layer preferably has the thickness of 5 μ m to 20 μ m.Even when said layer had so little thickness, said layer also can successfully stretch through using the thermoplastic resin base material.
Make up thickness (stretch before) preferred 50 μ m to the 250 μ ms of layered product with the thermoplastic resin base material.When thickness less than with 50 μ m the time, base material possibly break when stretching.In addition, the back thickness that stretches becomes so little, is difficult to carry so that layered product possibly become.When thickness surpasses 250 μ m, maybe over load be applied on the drawing machine.In addition, conveying possibly become difficult.
The thermoplastic resin base material uses the formation material to do, for example esters resin such as polyethylene terephthalate resinoid, cycloolefin resinoid, olefine kind resin such as polypropylene, polyamide-based resin, polycarbonate resin or its copolymer resin.Wherein, preferred cycloolefin resinoid (like norbornene resin) or amorphous polyethylene terephthalate resinoid.The resinoid instantiation of amorphous polyethylene terephthalate comprises and further comprises m-phthalic acid as the multipolymer of dicarboxylic acid and further comprise the multipolymer of cyclohexanedimethanol as dibasic alcohol.
The thermoplastic resin base material preferably has 170.Glass transition temperature below ℃ (T g).The use of this type of thermoplastic resin base material can not carried out the such temperature stretched layered product of the resinoid crystallization of PVA fast, and can suppress because the problem that crystallization produced (as suppress the orientation of PVA resinoid layer through stretching).It should be noted that the value of glass transition temperature (Tg) for measuring according to JIS K 7121.
Admissible any appropriate method is as the method that forms PVA resinoid layer.Preferable methods relate to comprise on the resinoid coating fluid paint of the PVA thermoplastic resin base material and dry liquid so that form PVA resinoid layer.It should be noted that thus obtained PVA resinoid layer not only can be used as layered product (on being formed at the thermoplastic resin base material time), also can be used as the PVA based resin film after peeling off from the thermoplastic resin base material.
Coating fluid typically is through the PVA resinoid is dissolved in prepared solution in the solvent.The instance of solvent comprises water, dimethyl sulfoxide (DMSO), dimethyl formamide, dimethyl acetamide, N-Methyl pyrrolidone, various dibasic alcohol, polyvalent alcohol such as trimethylolpropane and amide-type such as ethylenediamine and diethylene triamine.These solvents can be used alone or in combination.Wherein, preferred water.Solution preferably has the PVA resinoid concentration of 3 weight portion to 20 weight portions with respect to 100 parts by weight solvent.Such resin concentration can form the homogeneous that closely contacts with the thermoplastic resin base material and film.
Coating fluid can with the adjuvant compounding.The instance of adjuvant comprises plastifier and surfactant.The instance of plastifier comprises polyvalent alcohol such as monoethylene glycol and glycerine.The instance of surfactant comprises non-ionic surfactant.For the purpose of homogeneity, dyeability or the stretchability of additional improvement PVA resinoid layer to be obtained can be used these adjuvants separately.
Admissible any appropriate method is used rubbing method as coating fluid.The example comprises rolling method, spin-coating method, coiling rod rubbing method, dip coating, mold pressing rubbing method, curtain formula rubbing method, spraying process and scraper rubbing method (comma rubbing method etc.).
Baking temperature preferably is equal to or less than the glass transition temperature (Tg) of thermoplastic resin base material, and more preferably is equal to or less than Tg-20 ℃.Under this temperature, carry out drying and can prevent that the thermoplastic resin base material from forming preceding distortion at PVA resinoid layer, therefore can prevent the deterioration of the orientation character of PVA resinoid layer to be obtained.
B-2. stretch
The Nz coefficient can be controlled through suitably selecting stretching condition such as drawing process, draw ratio and draft temperature.The instance of drawing process comprises that the stiff end that relates to use tentering (tenter) drawing machine stretches, relates to the free end that uses the roller with different circumferential speed and stretches, relates to and use the biaxial stretch-formed and successively biaxial-oriented of synchronous twin shaft drawing machine.Can adopt these methods alone or in combination.Particularly; As shown in Figure 3; When PVA resin film 10 passes roller 31,31,32,32 with different circumferential speed so that when throughput direction (MD) stretches (free end stretchings), provided the embodiment of the stretching that combines perpendicular to the stretching of the direction (TD) of throughput direction with the edge.Hereinafter, specifically describe preferred embodiment.
In preferred embodiments, light polarizing film of the present invention is through shrinking the PVA resin film and producing along this film of second direction stretching along first direction.According to this working method, can successfully satisfy the Nz coefficient.
In one embodiment, first direction is the throughput direction (MD) of PVA resin film.The longitudinal direction of the preferably long PVA resin film of throughput direction, and can be regarded as from the longitudinal direction of PVA resin film-5 ° to+5 ° direction counterclockwise.In another embodiment, first direction is the direction (TD) vertical with throughput direction.The horizontal direction of the preferably long PVA resin film of the direction vertical with throughput direction, and can be regarded as from counterclockwise 85 ° to the 95 ° direction of the longitudinal direction of PVA resin film.It should be noted that term as used herein " vertically " is interpreted as the said direction situation of perpendicular each other.Here, term " perpendicular " is interpreted as that the angle between the said direction is 90 ° ± 5.0 °, preferred 90 ° ± 3.0 ° of angle, more preferably 90 ° ± 1.0 ° situation.
Contraction can be carried out with stretching simultaneously, or can carry out in any other time.In addition, the qualification especially of order of shrinking and stretching, and shrink and can carry out a stage, or can carry out in a plurality of stages.In one embodiment, the PVA resin film is shunk stretches along second direction simultaneously along first direction.In another embodiment, the PVA resin film was shunk before stretching along second direction along first direction.
In this embodiment, through adjustment, for example the shrinkage factor of PVA resin film can successfully satisfy the Nz coefficient.The PVA resin film is preferred below 40% along the shrinkage factor of first direction, and is more preferably below 35%, preferred especially below 20%.This is owing to can realize excellent permanance.Simultaneously, shrinkage factor is preferably more than 5%.When shrinkage factor foreshortens to 5%, maybe not can obtain sufficient optical characteristics.
Second direction can be depending on desired light polarizing film and is made as any suitable direction.Preferred second direction and first direction are perpendicular to one another.Particularly, when first direction was the throughput direction (MD) of PVA based resin film, second direction was preferably the direction vertical with throughput direction (TD).When first direction was the direction (TD) vertical with throughput direction, second direction was preferably throughput direction (MD).It should be noted that second direction is essentially the absorption axes direction of light polarizing film to be obtained.
The stretching of PVA resin film can be carried out a stage, or can carry out in a plurality of stages.But, below be the product of draw ratio in each step with the draw ratio of the PVA resin film of describing when when a plurality of stages stretch.In addition, the stretch mode in this step does not limit especially, and can be (dry type stretching) pattern that stretches in midair, or can be (wet type stretching) pattern that stretches in the water.
Draft temperature can be depending on, and for example stretch mode and stretching are to being made as any suitable value as thing.For example, when according to the layered product of stretch mode stretched thermoplastic resin base material in midair and PVA resinoid layer, draft temperature can be depending on, and for example the thermoplastic resin base material is with the formation material and be made as any suitable value.Draft temperature typically is equal to or greater than the glass transition temperature (T g) of thermoplastic resin base material, and the glass transition temperature (Tg) that is preferably greater than the thermoplastic resin base material more preferably is equal to or greater than T g+15 ℃ more than 10 ℃.Simultaneously, draft temperature is preferred below 170 ℃.Under this temperature, stretch and to suppress carrying out fast of PVA resinoid crystallization, and therefore can suppress because the problem (like breaking of PVA resin film when the PVA resin film stretches) that crystallization caused.
When according to stretch mode stretching PVA based resin film in midair, draft temperature typically is 70 ℃ to 130 ℃, preferred 80 ℃ to 120 ℃.
During stretch mode, draft temperature is preferred below 85 ℃, more preferably 30 ℃ to 65 ℃ in adopting water.When temperature surpasses 85 ℃, can cause the stripping of the iodine that the PVA resinoid adsorbs or the problem of the resinoid stripping of PVA, and therefore can reduce the optical property of light polarizing film to be obtained.
During stretch mode, the PVA resin film preferably stretches in the WS of boric acid in adopting water.For the PVA resin film, the use of the WS of boric acid can be given to be enough to resist the rigidity of tension force to be used and make film be not dissolved in the water tolerance of water when it stretches.Particularly, boric acid can produce the tetrahydroxy acid anion so that crosslinked through hydrogen bond and PVA resinoid in the WS, therefore can give rigidity and water tolerance.As a result, for example can reach the realization of extra high light polarizing film contrast ratio.Through boric acid and/or borate are dissolved in the WS that obtains boric acid in the water as solvent.The concentration of boric acid is 1 weight portion to 10 weight portion with respect to 100 weight parts waters typically.The PVA resin film is immersed in preferably about 15 seconds to 5 minutes of the time in the stretch bath.
Draw ratio along second direction is preferred more than 4.0 times with respect to the original length of PVA resin film.Contraction along first direction can stretch with so high ratio, therefore the light polarizing film with excellent optical can be provided.Simultaneously, draw ratio is preferred below 6.0 times, more preferably below 5.5 times.
Fig. 2 illustrates the instantiation of contraction-stretching step.In illustrative example, when its length direction is carried, PVA resin film 10 is stretched along the direction (TD) that throughput direction (MD) shrinks and the edge is vertical with throughput direction with synchronous twin shaft drawing machine at PVA resin film 10.Particularly, make at the PVA resin film 10 of tentering inlet to stretch, carry with preset speed simultaneously along TD with left and right sides intermediate plate (clip) 21,21 clampings.In illustrative example, the contraction of PVA resin film receives following control: for example reduce gradually each intermediate plate along the translational speed of throughput direction to shorten the distance between the intermediate plate.Shrinkage factor can receive following control: through adjustment along the distance L 1 between the intermediate plate of the tentering of throughput direction inlet with along the distance L 2 between the intermediate plate of the tentering outlet of throughput direction (along the translational speed of each intermediate plate of throughput direction).The speed of each intermediate plate that particularly, can be through being arranged on tentering outlet is that the product of speed and shrinkage factor of each intermediate plate of tentering inlet is realized the shrinkage factor expected.It should be noted that dotted line among Fig. 2 representes the track of intermediate plate 21.
When synchronous twin shaft drawing machine contraction of usefulness as shown in Figure 2 and stretching PVA resin film, the PVA resin film preferably shrinks before stretching.Particularly, shortening the distance between the throughput direction upper clip in the past along the TD stretched film.According to this embodiment, when stretching, apply power with extra homogeneous mode to the PVA resin film, therefore can prevent that the part of each intermediate plate clamping from optionally stretching.Particularly, can prevent not by the neck-in of the part of any intermediate plate clamping at the PVA resin film.As a result, can improve homogeneity.
B-3. other processing
Except that stretch processing, be used for being treated to of production light polarizing film, for example, dyeing processing, insoluble processing, crosslinking Treatment, carrying out washing treatment or dried.Can carry out any this type of processing at any reasonable time.
Dyeing is handled and typically is the processing that relates to dichroic substance dyeing PVA resin film.This processing is preferably through carrying out PVA resin film absorption dichroic substance.The method that is used to adsorb, for example, relate in comprising the dyeing liquor of dichroic substance dipping PVA resin film method, relate to dyeing liquor be applied to the method for PVA resin film or relate to the method with dyeing liquor spraying PVA resin film.Wherein, the method that preferably relates to dipping PVA resin film in comprising the dyeing liquor of dichroic substance.This is because dichroic substance can successfully be adsorbed to film.
When iodine was used as dichroic substance, dyeing liquor was preferably the WS of iodine.The compounding amount of iodine is 0.04 weight portion to 5.0 weight portion with respect to 100 weight parts waters preferably.The WS of iodine preferably with the salt compounded of iodine compounding so that can improve the solubleness of iodine in water.The instance of salt compounded of iodine comprises potassium iodide, lithium iodide, sodium iodide, zinc iodide, silver iodide, lead iodide, cupric iodide, barium iodide, calcium iodide, stannic iodide and titanium iodide.Wherein, preferred potassium iodide and sodium iodide.The compounding amount of salt compounded of iodine is 0.3 weight portion to 15 weight portion with respect to 100 weight parts waters preferably.
The fluid temperature of dyeing liquor is preferred 20 ℃ to 40 ℃ during dyeing.When the PVA resin film impregnated in the dyeing liquor, preferred 5 seconds to 300 seconds of the time of film immersion.With this understanding, can make the PVA resin film fully adsorb dichroic substance.
Typically carry out insoluble processing and crosslinking Treatment through dipping PVA resin film in the WS of boric acid.Typically carry out carrying out washing treatment through dipping PVA resin film in the WS of potassium iodide.Preferred 30 ℃ to 100 ℃ of baking temperature in the dried.
Hereinafter, via embodiment the present invention is described particularly.Yet the present invention does not receive the restriction of these embodiment.The method that it should be noted that the thickness of the light polarizing film that measurement obtains is described below.
(thickness of light polarizing film)
Handle PVA resinoid layer or PVA based resin film are measured in the back with clock gauge (being made ProductName " DG-205 type pds-2 " by PEAC OCK) thickness in the following dyeing that will describe.
[embodiment 1]
< production of layered product >
(thermoplastic resin base material)
The long cycloolefin based resin film (being made trade (brand) name " ARTON " by JSR) of Tg of thickness and 123 ℃ with 200 μ m is as the thermoplastic resin base material.
(preparation of coating fluid)
Polyvinyl alcohol (PVA) (PVA) resin (by Nippon Synthetic Chemical Industry Co., Ltd. makes, trade (brand) name " GOHSENOL (registered trademark) NH-18 ") with the degree of polymerization 1,800 and saponification degree 98 to 99% is dissolved in the water.Thus, preparation has the polyvinyl alcohol water solution of the concentration of 7 weight %.
(preparation of PVA resinoid layer)
The coating fluid paint is stood a surface (mold pressing rubbing method) of the thermoplastic resin base material of stretch processing with the mold pressing coating machine.Gains at 100 ℃ descended dry 180 second so that form PVA resinoid layer with thickness 9 μ ms thereafter.Thus, produce layered product.
< contraction-stretch processing >
As shown in Figure 2, make the gained layered product shrink 40% with synchronous twin shaft drawing machine at 140 ℃ of lower edge first directions (MD), simultaneously, it is stretched along second direction (TD) is dry with 5.0 times ratios.
< dyeing is handled >
Next, under 25 ℃, layered product impregnated in (iodine concentration: 0.5 weight %, potassium iodide concentration: 10 weight %) 30 seconds in the WS of iodine.
< crosslinking Treatment >
After the dyeing, under 60 ℃, layered product impregnated in (boric acid concentration: 5 weight %, potassium iodide concentration: 5 weight %) 60 seconds in the WS of boric acid.
< carrying out washing treatment >
After the crosslinking Treatment, under 25 ℃, layered product impregnated in (potassium iodide concentration: 5 weight %) 5 seconds in the WS of potassium iodide.
Thus, production has the light polarizing film of thickness 3 μ m on the thermoplastic resin base material.
Protectiveness film (thickness: 80 μ m, made trade (brand) name " TD 80UL " by Fujifilm Corporation) is adhered to the light polarizing film side of layered product through the vinyl alcohol bonding agent.Next, from light polarizing film, peel off the thermoplastic resin material, through the vinyl alcohol bonding agent protectiveness film (thickness: 40 μ m, by Toyo Kohan Co., Ltd. makes, trade (brand) name " Fine Cast ") is adhered to stripper surface then.Thus, produce the polarisation diaphragm.
[embodiment 2]
Except that following, use with embodiment 1 identical mode and produce the polarisation diaphragm: when producing layered product, form PVA resinoid layer with thickness 10 μ m; Shrinkage factor along first direction in contraction-stretch processing is made as 35%; And the concentration of iodine is made as 0.45 weight % when dyeing is handled.The thickness that it should be noted that the gained light polarizing film is 3 μ m.
[embodiment 3]
Except that following, use with embodiment 1 identical mode and produce the polarisation diaphragm: when producing layered product, form PVA resinoid layer with thickness 13 μ m; Shrinkage factor along first direction in contraction-stretch processing is made as 15%; And the concentration of iodine is made as 0.35 weight % when dyeing is handled.The thickness that it should be noted that the gained light polarizing film is 3 μ m.
[embodiment 4]
Except that following, use with embodiment 1 identical mode and produce the polarisation diaphragm: use PVA based resin film (by KURARAY C O., LTD. makes, trade (brand) name " P S-7500 ") to replace layered product with thickness 75 μ m; Shrinkage factor along first direction in temperature in contraction-stretch processing and the processing is made as 110 ℃ and 20% respectively; And the concentration of iodine is made as 0.2 weight % when dyeing is handled.The thickness that it should be noted that the gained light polarizing film is 19 μ m.
[embodiment 5]
Stand to dye, in the crosslinked and carrying out washing treatment; Be between 0.1 the roller at ratio with " L (interior)/W (next-door neighbour stretch before diaphragm width)) " to stretching distance; Make PVA based resin film (by KURARAY C O. with thickness 75 μ m; LTD. make trade (brand) name " P S-7500 ") stand wet type stretch (along the shrinkage factor of first direction (TD): 20%, along the draw ratio of second direction (MD): 5.0 times).Thus, production has the light polarizing film of thickness 19 μ m.Come production light polarizing film sheet through making in light polarizing film with those identical protectiveness adhesions of film of embodiment 1.It should be noted that except when dyeing is handled, the concentration of iodine being made as the 0.05 weight % those of the condition of dyeing, crosslinked and carrying out washing treatment and embodiment 1 are consistent.
(comparative example 1)
Except that following, use with embodiment 1 identical mode and produce the polarisation diaphragm: use PVA based resin film (by KURARAY CO., LTD. makes, trade (brand) name " PS-6000 ") to replace layered product with thickness 60 μ m; Be made as 110 ℃, 48% and 6.0 times respectively along the draw ratio along second direction in the shrinkage factor of first direction and this processing in temperature in contraction-stretch processing, this processing; And the concentration of iodine is made as 0.25 weight % when dyeing is handled.The thickness that it should be noted that the gained light polarizing film is 19 μ m.
(comparative example 2)
Except that following, use with embodiment 1 identical mode and produce the polarisation diaphragm: when producing layered product, form PVA resinoid layer with thickness 7 μ m; Shrinkage factor along first direction in contraction-stretch processing is made as 55%.The thickness that it should be noted that the gained light polarizing film is 3 μ m.
(comparative example 3)
Except that following, use with embodiment 1 identical mode and produce the polarisation diaphragm: when producing layered product, form PVA resinoid layer with thickness 15 μ m; In contraction-stretch processing, do not shrink (shrinkage factor is made as 0%) along first direction; And the concentration of iodine is made as 0.3 weight % when dyeing is handled.The thickness that it should be noted that the gained light polarizing film is 3 μ m.
The polarisation diaphragm that evaluation is obtained in each embodiment and comparative example.Evaluation method and evaluation criterion are described below.Table 1 illustrates measurement result.
1.PVA the Nz coefficient of resin film
(make with phase difference measuring apparatus by Oji Scientific Instruments; Trade (brand) name " KOBRA 31 * 100/IR ") be 848.2nm, 903.4nm, 954.7nm, 1 to 23 ℃ of following wavelength (λ); 000.9nm, 1; 045.9nm with 1, the phase differential of the arbitrary photo measure light polarizing film among the 089.0nm.Particularly; Under each wavelength, measure, use three-dimensional refractive index software for calculation (N-C alc.Ver.1.23) its Nz coefficient of pH-value determination pH then by the gained phase differential through film being inclined to and its absorption axes 30 ° of front phase differential (Re) and phase differential (R30) as sloping shaft.It should be noted that and repeatedly measure so that the coefficient of determination of curve of approximation becomes more than 0.9.
2. permanance
To on second direction (TD), have minor face test film (1,150mm * 650mm) from the polarisation diaphragm of gained, cut out.Prepare ten test films and be used for each embodiment and comparative example.Test film is adhered to contain the glass plate of contact adhesive.Gains are rested in the environment temperature stove jumpy, and the crackle generation ratio of back polarisation diaphragm is left standstill in inspection then.Be described below about the details of variation of ambient temperature, the calculating formula and the evaluation criterion of crackle generation ratio.
(details of variation of ambient temperature)
The circular in definition of " normal temperature → 85 ℃ → 45 ℃ → normal temperature " is 1 circulation, observes crackle takes place after 200 circulations existence or disappearance.It should be noted that 1 required time of circulation was made as 1 hour.
(calculating formula of crackle generation ratio)
Crackle generation ratio (%)=(sample number of crackle takes place)/10 * 100
(evaluation criterion)
◎: 0% to 10%
Zero: 20% to 30%
△: 40% to 50%
*: more than 60%
3. degree of polarization
(make with spectrophotometer by MURAKAMI COLOR RE SEARCH LABORATORY; Trade name " Dot-41 ") measures monolithic transmissivity (Ts), the parallel transmitance (Tp) of light polarizing film (polarisation diaphragm) and the transmitance (Tc) of intersecting, then by its degree of polarization (P) under the monolithic transmissivity of following standard test 40%.It should be noted that these transmitances are through coming measured value so that the Y value that colour correction obtains with the visual field twice (illuminant-C) of JIS Z 8701.
Degree of polarization (P)={ (Tp-Tc)/(Tp+Tc) }
1/2* 100
(evaluation criterion)
◎: more than 99.95%
More than zero: 99.93%
*: less than 99.9%
[table 1]
The polarisation diaphragm of each embodiment has been gathered excellent permanance and excellent optical.On the other hand, although this comparative example has high degree of polarization, each comparative example 1 and 2 permanance are low.The comparative example 1 that the thickness of light polarizing film is big has low especially permanance.Although comparative example 3 is excellent on permanance, this comparative example has low degree of polarization.
Each light polarizing film of the present invention and polarisation diaphragm are applicable to the for example liquid crystal panel of LCD TV, LCD, mobile phone, digital camera, video camera, portable game machine, auto-navigation system, duplicating machine, printer, facsimile recorder, clock and micro-wave oven.
Under situation about not departing from the scope of the present invention with spirit, many other modifications will be conspicuous, and can be easy to implemented by those skilled in the art.The scope that it is therefore to be understood that accompanying claims is not meant to the details that is subject to instructions, but should explain widely just the opposite.
Claims (8)
1. light polarizing film, it comprises the polyvinyl alcohol resin film that comprises dichroic substance, wherein said polyvinyl alcohol resin film has more than 1.10 to the Nz coefficient below 1.50.
2. light polarizing film according to claim 1, the degree of polarization of wherein said light polarizing film under 40% monolithic transmissivity is more than 99.9%.
3. light polarizing film according to claim 1, wherein said light polarizing film has the thickness less than 10 μ m.
4. light polarizing film according to claim 1, wherein said light polarizing film have the above thickness of 1 μ m.
5. light polarizing film according to claim 1; Wherein said light polarizing film is shunk along first direction through one of polyvinyl alcohol resin layer of making the polyvinyl alcohol resin film and on the thermoplastic resin base material, forming, and makes one of said film and said layer stretch and obtain along second direction.
6. light polarizing film according to claim 5, wherein the shrinkage factor along said first direction is to below 40% more than 5%.
7. light polarizing film according to claim 5, wherein the draw ratio along said second direction is more than 4.0 times.
8. polarisation diaphragm, it comprises:
Light polarizing film according to claim 1; With
Protectiveness film at least one side laminated of said light polarizing film.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-063850 | 2011-03-23 | ||
| JP2011063850A JP2012198449A (en) | 2011-03-23 | 2011-03-23 | Polarizing membrane and polarizing film |
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| Publication Number | Publication Date |
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| CN102692667A true CN102692667A (en) | 2012-09-26 |
| CN102692667B CN102692667B (en) | 2016-08-31 |
| CN102692667B9 CN102692667B9 (en) | 2016-11-23 |
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| CN201210080607.6A Active CN102692667B9 (en) | 2011-03-23 | 2012-03-23 | Light polarizing film and polarisation diaphragm |
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| Country | Link |
|---|---|
| US (1) | US9081146B2 (en) |
| EP (1) | EP2503365A1 (en) |
| JP (1) | JP2012198449A (en) |
| KR (1) | KR101430801B1 (en) |
| CN (1) | CN102692667B9 (en) |
| TW (1) | TWI461759B (en) |
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| CN104552908A (en) * | 2014-12-31 | 2015-04-29 | 张家港康得新光电材料有限公司 | Optical film, stretching manufacturing method and equipment thereof, and liquid crystal display equipment |
| CN108139533A (en) * | 2015-10-23 | 2018-06-08 | 住友化学株式会社 | The manufacturing method of stretched film and the manufacturing method of polarizing coating |
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| JP5371523B2 (en) * | 2009-04-14 | 2013-12-18 | 東芝機械株式会社 | Film stretching apparatus and film stretching method |
| KR20140015540A (en) * | 2011-06-20 | 2014-02-06 | 코니카 미놀타 가부시키가이샤 | Elongated polarization plate and liquid crystal display device |
| JP6172980B2 (en) | 2012-03-14 | 2017-08-02 | 日東電工株式会社 | Manufacturing method of liquid crystal display panel |
| JP6176827B2 (en) * | 2012-03-14 | 2017-08-09 | 日東電工株式会社 | Optical film roll |
| JP6112921B2 (en) * | 2012-03-14 | 2017-04-12 | 日東電工株式会社 | Manufacturing method of liquid crystal display panel |
| JP5860449B2 (en) * | 2013-11-14 | 2016-02-16 | 日東電工株式会社 | Polarizing film and manufacturing method of polarizing film |
| JP5932760B2 (en) | 2013-11-29 | 2016-06-08 | 住友化学株式会社 | Polarizer and polarizing plate including the same |
| JP6152127B2 (en) | 2015-02-16 | 2017-06-21 | 日東電工株式会社 | Polarizer, polarizing plate and image display device |
| JP2017003954A (en) * | 2015-06-12 | 2017-01-05 | 住友化学株式会社 | Polarizing film and polarizing plate including the same |
| KR20160146540A (en) * | 2015-06-12 | 2016-12-21 | 스미또모 가가꾸 가부시키가이샤 | Polarizing film and polarizing plate comprising the same |
| CN111045135B (en) * | 2018-10-15 | 2023-08-22 | 日东电工株式会社 | Polarizing plate with retardation layer and image display device using same |
| WO2020262399A1 (en) | 2019-06-28 | 2020-12-30 | ホヤ レンズ タイランド リミテッド | Method for manufacturing polarizing lens, polarizing film, and polarizing lens |
| WO2020262402A1 (en) * | 2019-06-28 | 2020-12-30 | ホヤ レンズ タイランド リミテッド | Method for manufacturing polarizing lens, polarizing film, and polarizing lens |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20120243089A1 (en) | 2012-09-27 |
| KR101430801B1 (en) | 2014-08-18 |
| EP2503365A1 (en) | 2012-09-26 |
| TW201248217A (en) | 2012-12-01 |
| CN102692667B9 (en) | 2016-11-23 |
| JP2012198449A (en) | 2012-10-18 |
| US9081146B2 (en) | 2015-07-14 |
| TWI461759B (en) | 2014-11-21 |
| CN102692667B (en) | 2016-08-31 |
| KR20120109362A (en) | 2012-10-08 |
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